Pressure-Controlled Layer-by-Layer to Continuous Oxidation of ZrS<inf>2</inf>(001) Surface

Understanding oxidation mechanisms of layered semiconducting transition-metal dichalcogenides (TMDC) is important not only for controlling native oxide formation but also for synthesis of oxide and oxysulfide products. Here, reactive molecular dynamics simulations show that oxygen partial pressure controls not only the ZrS2 oxidation rate but also the oxide morphology and quality. We find a transition from layer-by-layer oxidation to amorphous-oxide-mediated continuous oxidation as the oxidation progresses, where different pressures selectively expose different oxidation stages within a given time window. While the kinetics of the fast continuous oxidation stage is well described by the conventional Deal-Grove model, the layer-by-layer oxidation stage is dictated by reactive bond-switching mechanisms. This work provides atomistic details and a potential foundation for rational pressure-controlled oxidation of TMDC materials.